Extractive distillation of alcohols with glycols



y 3,1951 P. v. SMITH, JR., ETAL 2,559,520

EXTRACTIVE DISTILLATION OF ALCOHOLS WITH GLYCOLS 'Filed lay l, 1948 Consenszk "-F'2Ac1-\oNA-row.5-- 5 N2 255 cifzi o ri Uri-v enbors s-MMClbtornag Patented July 3, 1951 EXTRACTIV E DISTILLATION F ALCOHOLS WITH GLYCOLS Paul v. Smith, Jr., Westfield, and Carl s. Carlson,

Elizabeth, N. J.,

assignors to Standard'Oil Development Company, a corporation of Delaware Application May 1, 1948, Serial No. 24,497

This invention relates to a practical method of separating close-boiling oxygenated organic compounds and is concerned with the controlled use of a relatively high-boiling glycol as a refluxing medium in a continuous fractional distillation of the close-boiling oxygenated compounds.

In copending application, Serial No. 768,440, filed August 13, 1947, it is proposed to fractionate close-boiling oxygenated compounds byfractionally distilling the oxygenated compounds in 8 Claims. (Cl. 202-395) the presence of a large excess of a hydrocarbon oil which is liquid under the conditions obtaining in the fractionation zone. In such a system the volatilities of the compounds are altered to such an extent that separations are possible which are difiicult to obtain by ordinary fractionation.

There are, however, a number of disadvantages in employing straight hydrocarbons as a reflux medium in separating such oxygenated compounds. In the first place, solubility relationships are such that only small amounts of water can be present without separation of two liquid phases. Such liquid phase separation is generally quite undesirable in such systems since it results in loss of selectivity. Furthermore, in order to prevent entrainment of the hydrocarbon overhead with the alcohol products, both in the fractionation stage and in the subsequent stage of stripping the alcohol from the hydrocarbon, it is necessary to use a hydrocarbon of relatively high initial boiling point. This high initial boiling point of the hydrocarbon results in high tower temperatures and in the necessity for using large amounts of high pressure steam for reboiling.

It is, therefore, an object of this invention to provide a commercially feasible process for the eiiicient separation of close-boiling oxygenated compounds which are diflicult to separate by ordinary fractional distillation methods, while avoiding the difiiculties of limited miscibility and high boiling point encountered when using hydrocarbons as the refluxing medium.

The objects of this invention are accomplished by fractionating the mixture of close-boiling oxygenated compounds in the presence of a large excess of a glycol.

The process of this invention is best applied to distillation cuts or mixtures, the components of which distill within a narrow range; however, it may be applied to wide-boiling mixtures as well. The invention is particularly directed to the separation of alcohols of different types and molecular weights from one another and to the separation of alcohols as a class or one particular alcohol from other oxygenated compounds such as ketones, acetals, esters, aldehydes, etc., and is useful preferably in separating between compounds boiling in the range of normal propyl alcohol, secondary butyl alcohol and higher boiling compounds. Lower boiling mixtures cannot be separated without encountering reversal of :volatility. For'example, a mixture of ethanol and isopropanol cannot be separated by the present invention, without rendering isopropanol more volatile than ethanol. Typical separations which can be made are n-propyl alcohol from sec-butyl alcohol, n-propyl alcohol from i-butyl alcohol, n-propyl alcohol from a mixture of sec-butyl and i-butyl alcohols, n-propyl alcohol from methyl butyl ketone, n-propyl alcohol from valeraldehyde, n-propyl alcohol from a mixture of C4 andv higher molecular weight alcohols, and n-propyl alcohol from a mixture of C5 and higher molecular weight carbonyl compounds, and n-butyl alcohol from isomeric C5 and higher alcohols.

.The crude oxygenated mixture may contain amounts of water greater than, less than, or equal to the amounts corresponding to azeotropic compositions, but in any case it must be miscible with the solvent in all portions of the fractionation zone.

Some of the above-described mixtures are ob tained by an olefin hydration reaction, e. g., when a mixture of ethylene and propylene is absorbed in sulfuric acid, diluted, hydrolyzed, and a resulting aqueous alcohol mixture is stripped out. An-

other important source of such mixtures is the Fischer synthesis hydrogenation of carbon monoxide, especially when the aqueous layer product formed contains not only lower primary and sec ondary alcohols but also various ketones, aldehydes, ethers, acetals, esters, carboxylic acids and certain tertiary alcohols. Still another source is in the products of hydrocarbon oxidation where both oil and water layers are obtained, each containing oxygenated organic compounds. Narrow-boiling range mixtures which may be obtained by the ordinary distillation processes from aqueous solution are as follows:

The narrow-boiling range mixture may be a binary or tertiary mixture as in the groups shown, but generally the crude mixtures contain additional oxygenated organic compounds, which do not interfere with the basic operation of this in.- vention in isolating the principal alcohol components of the mixtures.

A typical propanol cut obtained from the water layer of a Fischer synthesis process contains the following:

TABLE II Normal propanol cut Binary Water Normal Boiling m. f??? Ethanol 7B. 5 78. Isopropanol. 82 4 80. n-Propanol 97. 8 87. seeButan 99. 5 87. iso-Butanol 107. 3 89. n-Butanol 117. 7 92. tert-Butanol 82. 8 79. iso-Propyl Acetate 89. 4 1 75. n-Propyl Acetate 101. 6 R2. Methyl Ethyl Ketone 79. 6 74. Methyl n-Propyl Ketone- 102 3 82.

' Methyl iso-Propyl Ketona. 94. 3 Diethyl Ketone 102. Methyl iso-Butyi Ketone 116. E Propiona 99.1 81.2 iso-Valeraldehyde. 92. 82 n-Valeraldehyde 103. 7 80. 6 Methyl n-Butyl Ketone 127. 2

1 Ternary with ethyl alcohol.

Table II which shows the overlapping of the anhydrous and binary aqueous azeotrope boiling points.

To obtain the desired separation of purified organic components from mixtures like that mentioned with benefits of the present invention, the mixture is subjected to a continuous fractional distillation in a column of practical size, including a primary rectification zone, a secondary rectification zone above the primary zone, and a.

stripping zone below the primary zone for countercurrent vapor liquid contact under reboiling and refluxing conditions. A suificiently large quantity of a glycol is introduced at the upper wonasuuororocnnmi part of the primary rectification zone to effectively modify the relative volatilities of the organic compounds to be separated and to distill a. larger part of one component or group of components than of another component or another group of components from the internal reflux.

The separation can be eilected in a continuous manner under steady state conditions to obtain product streams of desired purities and constant compositions while supplying'the large quantity of glycol to the upper part of the rectification zone. The temperature of the glycol introduced into the primary rectification zone is preferably close to the temperature of the liquid on its feed plate, although it may be lowered to partially condense vapors ascending to the solvent feed plate. 1

Since the efiicient operation is essentially continuous, the glycol is added continuously near the top of the primary rectification zone of the column while the mixture of oxygenated organic compounds to be separated is fed continuously into the column at a lower point while suflicient heat is provided to afford distillation throughout the column.

The feed stream of the oxygenated organic compounds is preferably introduced into the fractionating column between the primary rectification zone and the lower stripping zone at a point where the ratio of the main organic compounds to beseparated in the feed is similar to the ratio of these compounds in the internal reflux descending through the column.

The feed stream is preferably preheated to a temperature close to that of the internal liquid reflux under practically equilibrium boiling conditions at the point of introduction. The preheated feed stream may be liquid, partially vaporized, or completely vaporized when introduced into the fractionating column.

Vapors of the organic compounds introduced as a feed stream at the bottom part of the primary rectification zone in the fractionating column pass up through the primary rectification zone in contact with descending intemal liquid reflux under practically equilibrium reboiling and refluxing conditions. Thesecondary rectification zone serves to strip glycol from the overhead vapors.

The quantity of glycol required to be introduced continuously at the upper part of the primary rectification zone for accomplishing the desired separation of the close-boiling compounds is considerably greater than the quantity of condensate with which it becomes homogeneously mixed. This is necessary in order to make the glycol concentration of the internal reflux substantially above a critical minimum in the range of -99 volume percent. With adequate glycol concentration in the internal reflux for effecting the separation, the organic component to be isolated in the bottoms is dissolved in the internal reflux that reaches the bottom part of the primary rectification zone and finally the bottom of the stripping zone.

The minimum concentration in the internal reflux of the glycol for obtaining the separation depends on the particular organic compounds to be separated and varies between '70 and 99 volume percent. In a limiting case of isolating n-propyl alcohol from sec-butyl alcohol, essentially no separation is effected if the internal reflux contains less than volume percent glycol, and for obtaining satisfactory results on a practical scale, more than volume percent glycol, preferably 90-99 volume percent, is required in the internal liquid reflux. As the dilution of the internal reflux becomes infinite, the selectivity of separation is increased but the operating efliciency is excessively lowered on account of the relatively small quantities of the oxygenated organic compounds being processed.

Under steady state conditions existing in a continuously operating fractional distillation zone, the internal reflux having adequate concentration for accomplishing the separation of the close-boiling alcohols and other oxygenated compounds. there tends to be a nearly constant glycol concentration in the homogeneous liquid phase on each plate above the feed point and on each plate below the feed point although the average concentration on the plates above and below the feed point may differ. This internal reflux in flowing from the top to the bottombeab-tame comes richer in the oxygen compounds having. the lowest relative volatility in the presence of the glycol, while the oxygen compounds having the highest relative volatility in the glycol are distilled overhead.

The overhead vapors from the secondary rectification zone are enriched in one or more of the organic components rendered relatively more volatile by concentration of the glycol in the liquid reflux while the remaining portion of the Organic material introduced with the feed remains dissolved in the internal reflux. For example, in distilling an aqueous mixture of two alcohols the distillation may be carried out so that either one of the alcohols is obtained free of the other. In separating n-propanol from secondary butanol, the distillation may be conducted so that n-propanol is obtained overhead and a mixture of n-propanol and sec-butanol is obtained in the bottoms or a portion of the secondary butanol may be taken overhead with the n-propanol so that secondary butanol free of n-propanol is obtained in the bottoms.

The functioning of the stripping zone'may be described as follows:

The mixture of the close-boiling alcohols and other oxygenated compounds to be separated, as in the liquid reflux from the bottom of the rectification zone, flows downwardly through the stripping zone in countercurrent contact with ascending vapors evolved from the solution under reboiling conditions. A sufliciently high concentration of glycol is maintained in the liquid flowing down through the stripping zone, as in 'the rectification zone, to make the liquid progressively richer in oxygenated compounds havin the lowest relative volatility in the glycol while the oxygenated compounds having the highest relative volatility in the glycol are stripped from the liquid. Under practically equilibrium reboiling and refluxing conditions for complete stripping in the stripping zone, the organic compounds rendered more volatile may be removed as vapor overhead from the stripping zone at the 'same rate that they enter the stripping zone as part of the liquid feed to this zone and a solution of the organic compounds rendered less volatile, freed of the more volatile compounds in the liquid, may be withdrawn from a bottom part of the stripping zone.

Suitable glycols to be used in the process of the present invention include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2'and 1,3-butylene glycol, pentanediol-2,4, 2-ethylhexanediol-1,3, hexanediol-2,5, heptanediol-2,4, tetramethylene glycol, isobutylene glycol, 1,2 and 1,3-normal amylene glycol, pentamethylene glycol, dimethyl trimethylene glycol, 1,4 isoamylene glycol, pinacol, etc. I

In the accomplishment of the foregoing and related ends, the invention then comprises the features hereinafter fully described, and particularly pointed out in the claims, the following description and the annexed drawing setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principle of the invention may be employed.

This invention will be described in detail as applied to the separation of n-propyl alcohol and sec-butyl alcohol from aqueous solution.

Referring to the drawing, a feed fraction is introduced by line 3 into the'tower I where it is fractionated in the presence of a liquid stream 6 of .a glycol introduced through line 4, at a point several plates below the top of the tower. The conditions in the tower are such as to cause a distillation of the alcohol compounds in the presence of the glycol on each plate of the tower. A sumcient amount of the glycol is added so that it is boiling points and are continuously being contacted with'vapors boiled from the plates below. Because of the enhanced volatility of the n-propyl alcohol in relation to the sec-butyl alcohol the vapors are relatively rich in the former and poor in the latter. By maintaining the amount of glycol on each plate so large that infinite dilution is approached, the optimum relative volatilities for the separation of the desired components can be secured. Furthermore, by controlling the amount of oxygenated compound reflux and consequently the reflux ratio and the number of plates, the actual degree of separation may be varied until the desired product purity and recovery are obtained. Thus, suitable temperature and reflux conditions are maintained in the tower so that substantially pure n-propyl alcohol appears in the overhead stream and a solution of sec-butyl alcohol in glycol appears in the bottom product. The plates above the point of glycol entry-serve to strip glycol from the alcohol overhead. Any water present in the feed will appear with the overhead alcohol product.

Overhead vapors consisting substantially of pure n-propanol and all the water entering with the feed are withdrawn from the top of column I through line 5 by which they are passed through condenser 6 to a receiver I. A portion of the condensate collected in receiver 1 is returned to the top part of the column I as external reflux through line 8. The remaining portion of distillate collected in receiver 1 is withdrawn through line 9 as a product.

Bottoms liquid consisting of a solution of secbutyl alcohol in glycol collected at the lower part of column I is passed by line III into reboiler I I for heating by indirect or direct heat exchange with a heating medium such as live steam. A portion of the bottoms liquid heated and partially vaporized in the reboiler I I is recycled by line I2 to the lower part of column I. The remaining portion is withdrawn through line I3 to tower 2 where sec-butyl alcohol is separated from the glycol and removed overhead through line I4. Glycol is removed from the bottom of the tower through line I5 and recycled to tower I.

Representative data are given in the following tables showing the application of this invention to the separation of ethanol and isopropanol and of normal propanol and secondary butanol. The relative volatility given in the table is the volatility of one component divided-by that of the other, the volatility of each component being proportional to its partial pressure divided by its mol fraction in the liquid phase. It is also defined by the equation alpha=(y1/y2)/(:r1/xz) where y refers to the vapor phase mol fractions of the components to be separated and 3: refers to the liquid phase mol fractions of the components to be separated, subscript one designates the more volatile component and subscript two the less volatile component.

TABLE III Relative volatility of ethanol to isopropanol Run No. 1 2 a 4 Chage:

1 Per Cent EtOH V 80 80 20 80 M81 Per Cent i onl Basls- 2o 20 so 20 Vol. Per Cent 1.3-Butylene Glycol. 90 80 80 70 Sam le: lilo] Per Cent EtOH 77. 8 77. 6 l6. 6 77. 8

Mol. Per Cent IpOH 22. 2 22. 4 8i. 4 22. 2

uid Sam e:

Mol Pei-Cent EtOH 81.8 81.2 24.4 81. 6

Mol Per Cent IpOH 18. 2 18L 8 75. 6 18. 4 Relative Volatility of EtOH to IpOH. 0.780 0.892 0.617 0.834

Normal volatility in absence of solvent=EtH over IpOH, 1.15.

TABLE IV Relative volatility of normal propanol to secondary butanol 0lglormal volatility in absence of solvent? n-PrOH over sec-B11011. 1.

From the above data it is evident that the compounds of this invention are not suitable for the separation of ethanol from isopropanol due to the reversal of volatility but that the invention finds utility in separating normal propanol from higher boiling compounds.

The nature and objects of the present invention having been thus fully set forth and specific examples of the same given, what is claimed as new and useful and desired to be secured by Letters Patent is:

1. In a process of separating aqueous azeotropic mixtures of n-propyl alcohol and sec-butyl alcohol, the steps which comprise continuously passing a solution of n-propyl alcohol in a glycol containing sec-butyl alcohol down through a stripping zone so that a liquid portion of the solution flows countercurrently in contact with vapors evolved therefrom under constant refluxing and reboiling conditions, maintaining a sulficiently high concentration of solvent in the resulting internal reflux to effect vaporization of a larger part of the n-propyl alcohol than of the sec-butyl alcohol in said reflux, continuously withdrawing vapors of alcohols and water overhead from the stripping zone, the n-propyl alcohol being thus withdrawn as vapor at essentially the same rate that the n-propyl alcohol dissolved in said solvent enters the stripping zone and withdrawing from a bottom part of the stripping zone a solution of sec-butyl alcohol in the glycol substantially free of n-propyl alcohol and water.

2. In a process of separating normal propyl alcohol from its aqueous mixtures with saturated monohydric alcohols having four carbon atoms, the steps which comprise continuously passing a solution in a glycol of a mixture of normal propyl alcohol and alcohols containing four carbon atoms down through a stripping zone so that a liquid portion of the solution flows countercurrently in contact with vapors evolved therefrom under constant refluxing and reboiling conditions, maintaining a sufficiently high concentration of glycol in the resulting reflux to effect vaporization of a larger part of the normal propyl alcohol than of the higher boiling alcohols in said reflux, continuously withdrawing vapors or normal propyl alcohol and water overhead from the stripping zone, the normal propyl alcohol being thus withdrawn as vapor at essentially the same rate that the normal propyl alcohol dissolved in said solvent enters the stripping zone and withdrawing from a bottom part of the stripping zone a solution of alcohols containing four carbon atoms in the glycol substantially free of normal propyl alcohol and Water.

3. The method of separating lower and higher molecular weight saturated monohydric alcohols containing 3 to 5 carbon atoms per molecule and having normal boiling points above that of isopropanol and which form close-boiling mixtures diflicult to separate by ordinary fractional distillation, which comprises continuously introducing a feed mixture of said alcohols to a fractional distillation zone wherein vapors of said alcohols ascend countercurrently to liquid reflux of the alcohols dissolved in 70 to 99 volume percent of a glycol to efiect vaporization of lower molecular weight alcohol, continuously removing Vapor of lower molecular weight alcohol overhead from the fractional distillation zone and removing a solution of higher molecular weight alcohol in the glycol as bottoms.

4. A process according to claim 3 in which the alcohols in the feed mixture are aqueous alcohols.

5. A process according to claim 3 in which the alcohol feed mixture comprises normal propyl and secondary butyl alcohols and in which nor mal propyl alcohol is removed overhead and a solution of normal propyl alcohol and secondary butyl alcohol in the glycol is removed as bottoms.

6. A process according to claim 3 in which the glycol is ethylene glycol.

7. A process accordin to claim 3 in which the glycol is 1,3-butylene glycol.

8. A process according to claim 3 in which the concentration of the glycol in the internal reflux is to 99 volume percent.

PAUL V. SMITH, JR. CARL S. CARLSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Kyrides et al.: Dehydration of Alcohols with Alkali Metal Alcoholates." 24, Industrial and Engineering Chemistry, 795-797 (July 1932). Copy in Scientific Library. 

3. THE METHOD OF SEPARATING LOWER AND HIGHER MOLECULAR WEIGHT SATURATED MONOHYDRIC ALCOHOLS CONTAINING 3 TO 5 CARBON ATOMS PER MOLECULE AND HAVING NORMAL BOILING POINTS ABOVE THAT OF ISOPROPANOL AND WHICH FORM CLOSE-BOILING MIXTURES DIFFICULT TO SEPARATE BY ORDINARY FRACTIONAL DISTILLATION, WHICH COMPRISES CONTINUOUSLY INTRODUCING A FEED MIXTURE OF SAID ALCOHOLS TO A FRACTIONAL DISTILLATION ZONE WHEREIN VAPORS OF SAID ALCOHOLS ASCEND COUNTERCURRENTLY TO LIQUID REFLUX OF THE ALCOHOLS DISSOLVED IN 70 TO 99 VOLUME PERCENT OF A GLYCOL TO EFFECT VAPORIZATION OF LOWER MOLECULAR WEIGHT ALCOHOL, CONTINUOUSLY REMOVING VAPOR OF LOWER MOLECULAR WEIGHT ALCOHOL OVERHEAD FROM THE FRACTIONAL DISTILLATION ZONE AND REMOVING A SOLUTION OF HIGHER MOLECULAR WEIGHT ALCOHOL IN THE GLYCOL AS BOTTOMS. 